Coating composition



United States Patent 3,207,611 COATING CUMPOSITION Irwin R. Ehren,Cleveland Heights, Ohio, assignor to The Lubrizol Corporation,Wicklitfe, Ohio, a corporation of Ohio No Drawing. Filed Jan. 3, 1962,Ser. No. 164,145 13 Claims. (Cl. 106-14) The present invention relatesto a fluid composition adapted to provide an electrically conductive,protective coating for meals. In a more particular sense, it relates toa fluid composition adapted to provide a weldable protective coating forferrous metals.

It is common practice in the automotive industry to coat various ferrousundercarriage parts of passenger cars and trucks such as brackets,box-channels, panels, and braces with a suspension of Zinc dust in anorganic vehicle, generally an alkyd or synthetic resin. Somemanufacturers depart from this practice in that they prefer to coatferrous metal stock with the zinc-filled organic vehicle before it isformed into the various parts. In any event, they all seek to providethese ferrous parts with a coating which protects the parts fromcorrosion and which, at the same time, does not impair the weldabilityof the coated ferrous surface.

The zinc-filled organic vehicles, i.e., zinc-filled paints, presentlyavailable for this purpose have not been fully satisfactory. They haveafforded only limited protection against corrosion although they havebeen satisfactory with respect to weldability. In an effort to improvecorrosion resistance, some manufacturers have first treated the ferrousparts and/or ferrous stock from which the parts are made with an aqueousphosphating solution to form thereon an integral inorganic phosphatecoating and thereafter applied a zinc-fillled paint over the phosphatecoating. Although a significant improvement in corrosion resistance isobtained by such a two-step procedure, the increased handling andprocessing costs have seriously limited its wide-spread application.

It is an object of the present invention to provide a fluid compositionwhich forms a protective, adherent, easily Weldable coating on metalsurfaces.

Another object is to provide a composition particularly adapted toprevent the corrosion of ferrous metal surfaces.

Still another object is the provision of corrosion-resistant, weldableferrous articles.

According to the present invention these and other objects are achievedby means of a fluid composition adapted to form a protective coating onmetals which contains as essential ingredients:

(A) Finely divided zinc, (B) A metal-containing organic phosphatecomplex prepared by the process which comprises the reaction of (I) Apolyvalent metal salt of the acid phosphate esters derived from thereaction of a phosphoruscontaining reagent selected from the groupconsisting of phosphorus pentasulfide and phosphorus pentoxide with amixture of monohydric and polyhydric alcohols, and (II) At least about0.1 equivalent of an organic epoxide, and (C) A metal-free organicphosphate complex prepared by the process which comprises mixing onemole of phosphorus pentoxide, from about 0.2 to about 12.5

moles of a copolymer of allyl alcohol and a styrene,

and from about 0.3 to about 50 moles of an alkyl phenol, and heatingsaid mixture at a temperature within the range from about 75 C. to about150 C.

In addition to these characterizing ingredients, the fluid compositionwill also generally contain a viscosity-reducing amount of a volatilesolvent and a pigment-suspending 3,207,611 Patented Sept. 21, 1965 agentsuch as castor Wax or a polyvalent metal stearate to prevent thesettling and agglomeration of the zinc dust into a hard,difiicultly-dispersible precipitate. For obvious practical reasons,then, it is generally highly desirable to include both apigment-suspending agent and a volatile solvent in the fluidcomposition-s of this invention.

INGREDIENT (A) Ingredient (A), the finely-divided zinc, is preferablycommercial powdered zinc passing 325-mesh screen according to ASTM testE 1158T. Powdered zinc of such fineness is more readily dispersed withthe other ingredients of the composition than is a coarser grade and,furthermore, shows less tendency to precipitate upon storage.

INGREDIENT (B) Ingredient (B), the metal-containing organic phosphatecomplex prepared by the reaction of an organic epoxide with a polyvalentmetal salt of the acid phosphate esters derived from the reaction ofphosphorus pentasulfide and/ or phosphorus pentoxide with a mixture ofmonohydric and polyhydric alcohols, is described in detail in US. Patent2,820,723 to W. M. Le Suer and in co-pending application Ser. No.139,845, filed September 22, 1961. In the interest of not undulylengthening the present application it is intended that the entiredisclosures of the aforesaid patent and pending application beincorporated herein by reference. It should also be noted that the termphosphate as used herein is intended to be generic to both oxyphosphatesand phosphorothioates.

The patent to Le Suer is concerned with the reaction of an organicepoxide with a metal phosphorodithioate, especially a zincphosphorodithioate derived from the neutralization of aphosphorodithioic acid prepared from the reaction of phosphoruspentasulfide with a mixture of monohydric and polyhydric alcohols.

Application Ser. No. 139,845 describes a metal-containing organicphosphate complex prepared by the reaction of an organic epoxide with apolyvalent metal salt of the acid oxyphosphate esters derived from thereaction of phosphorus pentoxide with a mixture of monohydric andpolyhydric alcohols.

The monohydric alcohols useful in the preparation of ingredient (B) areprincipally the non-benzenoid alcohols, i.e., the aliphatic andcycloaliphatic alcohols, although in some instances aromatic and/ orheterocyclic substituents may be present. Thus, suitable monohydricalcohols are, e.g., propyl, isopropyl, butyl, isobutyl, amyl, hexyl,cyclohexyl, heptyl, methylcyclohexyl, octyl, isooctyl, decyl, lauryl,tridecyl, oleyl, benzyl, betaphenethyl, alpha-pyridylethyl, etc.,alcohols. In some instances it is also desirable to use aromaticalcohols, i.e., phenols, such as, e.g., phenol, cresol,tertiary-butylphenol, isooctylphenol, and the like. Mixtures of suchalcohols can also be used if desired. Substituents such as e.g., chloro,bromo, fluoro, nitro, nitroso, ester, ether, sulfide, keto, etc., whichdo not prevent the desired reaction, may also be present in the alcohol.In most instances, however, the monohydric alcohol will be anunsubstituted alkanol.

The polyhydric alcohols useful in the preparation of ingredient (B) areprincipally glycols, i.e., dihydric alcohols, although trihydric,tetrahydric, and higher polyhydric alcohols may also be used. In certaininstances, they may contain aromatic and/ or heterocyclic substituentsas well as chloro, bromo, fluoro, nitro, nitroso, ether, ester,sulfides, keto, etc., substituents. Thus suitable polyhydric alcoholsare, e.g., ethylene glycol, diethylene glycol, triethylene glycol,propylene glycol dipropylene glycol, 1,3-butanediol, glycerol, glycerolmonooleate, monophenyl ether of glycerol, mono-benzyl ether of glycerol,1,3,5-hexanetriol, pentaerythritol, sorbitol dioctanoate,pentaerythritol dioleate, and the like. In some instances,

it is also desirable to use polyhydric aromatic alcohols, i.e.,polyhydric phenols, such as, for example, hydroquinone, catechol, andthe various alkylidene bisphenols such as, e.g., 4,4-methylene.bisphenol, 4,4-propylidene bisphenol, and the like.

The alcohol mixture may contain a single monohydric and a singlepolyhydric alcohol, or a plurality of one or both of such alcohols. Forthe purpose of this invention, best results are achieved when there ispresent from 0.25 to about 4.0 equivalents of polyhydric alcohol perequivalent of monohydric alcohol. The term equivalent as used hereinreflects the hydroxyl equivalency of the alcohol. Thus, for example, onemole of octyl alcohol is one equivalent thereof, one mole of ethyleneglycol is two equivalents thereof, one mole of glycerol is threeequivalents thereof, etc. The use of mixtures outside of this rangetends to produce either intractable esters, or esters which, whenconverted in ingredient (B), are deficient in film-forming properties.Mixtures of isooctyl alcohol and dipropylene glycol are verysatisfactory and a particular preference is expressed for a mixture inwhich these alcohols, respectively, are present in about equivalentamounts.

The reaction between the alcohol mixture and phosphorus pentoxide and/orphosphorus pentasulfide is exothermic and can be carried outconveniently at a temperature ranging from room temperature or below, toa temperature just beneath the decomposition point of the mixture.Generally reaction temperatures within the range from about 40 C. toabout 200 C. are most satisfactory. When phosphorus pentasulfide is usedthe temperature is preferably kept below 140 C. to avoid decompositionof the acid thioesters formed. Such precautions are not necessary whenphosphorus pentoxide is used since the acid oxyesters formed are muchless susceptible to decomposition than the acid thioesters. The reactiontime required varies according to the temperature, thephosphorus-containing reagent employed,'and the hydroxyl activity of thealcohol mixture. At the higher temperatures, as little as 5 or minutesmay be sufficient for complete reaction. On the other hand, at roomtemperature 12 or more hours may be required. Generally it is mostconvenient to heat the alcohol mixture with phosphorus pentoxide and/orphosphorus pentasulfide. for 0.5 to 8 hours at 60- 120 C. In any event,the reaction is carried out until periodic acid number determinations onthe reaction mass indicate that no more acid phosphate esters are beingformed.

To facilitate mixing and handling, the reaction may be conducted in thepresence'of an inert solvent. Generally such solvent is a petroleumdistillate hydrocarbon, an aromatic hydrocarbon, an ether, or a lowerchlorinated alkane, although mixtures of any such solvents can be used.Typical solvents include, e.g., petroleum aromatic spirits boiling inthe range 250-400 F., benzene, xylene, toluene, mesitylene, ethylenedichloride, diisopropyl ether, etc. In most instances, the solvent ispermitted to remain in the acid phosphate esters and ultimately thefinal metal.- containing organic phosphate complex, where it serves as avehicle for the convenient application of films of the fluidcompositions of this invention to metal surfaces.

The reaction of phosphorus pentasulfide with alcohols or phenols isknown to produce organic phosphorodithioic acids. The stoichiometry ofthis reaction is likewise wellknown; it involves the reaction of onemole of phosphorus pentasulfide with 4 equivalents of an alcohol ormixture of alcohols. Lesser or greater amounts of alcohol can be used,e.g., from about 2 to about 6 or more equivalents, but in such instancesthere is'generally either incomplete reaction or an excess of thealcohol remains as the diluent in the product. For the purpose of thepresent invention, it is contemplated to use from about 2 to about 6 ormore equivalents of alcohol per mole of phosphorus pentasulfide,although it is usually preferred to use the stoichiometric proportionsof 4 equivalents to 1 mole, respectively, in the interest of convenienceand economy.

The reaction of phosphorus pentoxide with alcohols is 4 known to producea mixture of oxyphosphate esters consisting principally of acidoxyphosphate esters of the general formula:

where x equals one or two and R is an organic radical, although someneutral triesters of the formula (RO) PO may also be formed. Thestoichiometry of this reaction is not clear; no equation can be givenwhich indicates the precise nature and amounts of the acid oxyphosphateesters formed. In any event, a complex mixture of different esters isalways obtained, the relative proportions of which can be altered byvarying the amount of alcohol used from about 2 to about 6 or moreequivalents per mole of phosphorus pentoxide. For the purpose of thepresent invention, it is generally preferred to employ from about 3 toabout 5 equivalents of the alcohol mixture per mole of phosphoruspentoxide.

In lieu of either phosphorus pentoxide or phosphorus pentasulfide, amixture thereof may be used in reaction with the.mixture of monohydricand polyhydric alcohols. In such instances, a complex mixture of acidesters of both oxyphosphoric and phosphorodithioic acids results. Theuse of phosphorus oxysulfides such as, e.g., P O S is likewisecontemplated since they are deemed to be the equivalent of mixtures of P8 and P 0 for the purpose of this invention.

The conversion of the acid phosphate esters to .the polyvalent metalsalt may be carried out by any of the various known methods for thepreparation of salts of organic acids such as, e.g., reaction of theacid esters with a polyvalent metal base such asa metal oxide,hydroxide, or carbonate. Other suitable methods include, e.g., reactionof the acid esters with a finely-divided polyvalent metal, orthemetathesis of a monovalent metal salt of the acid esters with a solublesalt of the polyvalent metal such as, e.g., a nitrate, chloride, oracetate thereof.

The polyvalent metal of ingredient (B) may be any light or heavypolyvalent metal such as, e.g., zinc, cadmium, lead, iron, cobalt,nickel, barium, calcium, strontium, magnesium, copper, bismuth, tin,chromium, or manganese. A preference is expressed for the polyvalentmetals of Group II of the Periodic Table and of these, zinc isparticularly preferred.

A highly etfective starting material for the preparation of ingredient(B) of the present invention is the zinc salt .ofthe acid oxyphosphateesters formed by the reaction of a mixture of equivalent amount ofisooctyl alcohol and dipropylene glycol with phosphorus pentoxide.Another related and highly effective starting materialis prepared in thesame manner, except that phosphorus pentasulfide is used in lieu ofphosphorus pentoxide.

The formation of the metal-containing organic phos phate complex used asingredient (B) of this invention involves, as indicated, a reactionbetween the polyvalent metal salt of certain acid phosphate esters andan organic epoxide. The organic epoxides, i.e., compounds containing atleast one linkage where x is zero or a small integer, suitable for thepreparation of ingredient (B) include the various substituted andunsubstituted alkyline oxides containing at least two aliphatic carbonatoms, such as, e.g., ethylene oxide, 1,2-propylene oxide, 1,3-propyleneoxide, 1,2-butylene oxide, pentamethylene oxide, hexamethylene oxide,1,2-octylene oxide, cyclohexene oxide, methylcyclohexene oxide,1,2;11,12 diepoxydodecane, styrene oxide, alpharnethyl. styrene oxide,beta-propiolactone,methyl epoxycaprylate, ethyl epoxypalmitate, propylepoxymyristate, butyl epoxystearate, epoxidized soyabean oil, and thelike. Of the various available organic epoxides, it;is preferred to usethose which contain at least three carbon atoms. p i lly preferred arethose p x des which contain at least 12 carbon atoms and also acarboxylate group in the molecule. Thus, the commercially availableepoxidized carboxylic ester, butyl epoxystearate, and epoxidizedsoyabean oil are very satisfactory epoxides for the preparation ofingredient (B). The low molecular weight carboxylic acid-epoxide,beta-propiolactone, is likewise useful for the preparation of ingredient(B) herein, especially when it is used in combination with a highmolecular weight epoxide such as, e.g., butyl epoxystearate. If desired,the organic epoxide may also contain substituents such as, e.g., chloro,bromo, fiuoro, nitro, nitroso, ether, sulfide, keto, etc., in themolecule.

The stoichiometry of the reaction of the polyvalent metal salt of theacid phosphate esters with the organic epoxide to form themetal-containing organic phosphate complex used as ingredient (B) hereinis not precisely known. There are indications, however, that the reaction involves about one equivalent each of the polyvalent metal salt andthe organic epoxide (for this reaction, one equivalent of an epoxide isthe same as one mole thereof). This is not to say that complexes madefrom one equivalent of the polyvalent metal salt and less than or morethan one equivalent of the organic epoxide are unsuited for the purposeof this invention. Complexes pre pared using as little as 0.1 or 0.25equivalent or as much as 1.5 to 2 or more equivalents of the organicepoxide per equivalent of polyvalent metal salt are satisfactory for useas ingredient (B). For reasons of economy and optimum corrosioninhibition, however, it is usually pre- Table 1 Metal containing organicphosphate derived from- Example No. of U.S.

2,820,723 Zinc salt of the phosphorodithioic Equivaacid prepared fromEquiva- Organic epoxide lents the reaction of P 8 lents with- 1Equivalent 1. Butylene oxide 1. 0

amounts of isooctyl alcohol and propylene glycol. do 1. 0 Butylepoxy- 1. 0

stearate. A 1:3 equivalent 1. 0 Butylene oxide 1. 0

mixture of isooctyl alcohol and propylene glycol. 4 do 1. 0 Butylepoxy- 1. 0

stearate. 5 Equivalent 1. 0 Dodecenc oxide 1. 0

amounts of isooctyl alcohol and ethylene glycol. 6 do 1. 0 Epoxyamyl 1.0

propyl sulfide.

Specific examples of metal-containing organic phosphate complexes whichare disclosed in detail in application Ser. No. 139,845 and which arealso useful as ingredient (B) herein are shown in Table 2.

Table 2 Metal-containing organic phosphate complex derived from ExampleNo. Metal salt of oxyphosphate acid esters in Ser. No.

139,845 Organic epoxide Equivalents Acid esters derived from MetalEquivalents reaction of P 0 with- 1 Equivalent amounts of iso Zn 1. 0Butyl epoxystearate.-- 1. 0

oetyl alcohol and dipropylene glycol. 2 (lo Cd 1.0 1.0 t 1. 0 1. 0 4 1.0 1. 0 1. 0 1. 0 6 0. 34 0. 34 7 0. 52 Butyl epoxystearat 0. 52 8 0. 52Beta-propiolaetone 0. 52 9. 0. 19 Butyl epoxystearate... 0. 19 10 Z 1. 01,2propylene oxide 1. 0 11 Equivalent amounts of Zn 1. 0 Butylepoxystearatc. 1. 0

yl alcohol and diethylene glycol. 12 A 4:1 equivalent mixture Zn 1. 0do 1. 0

of n-decanol-l and pentaerythritol.

ferred to use about equivalent amounts of the two starting materials.

The reaction between the organic epoxide and the polyvalent metal saltof the acid phosphate esters is only slightly exothermic, so in order toinsure complete reaction some heat is generally supplied to the reactionmass. The time and temperature for this reaction are not particularlycritical; satisfactory results may be obtained by maintaining the massfor 0.5-6 hours at a temperature within the range from about C. to about150 C. Ordinarily, the product is clear and does not require afiltration. In some instances, however, it is desirable to filter theproduct, particularly when the polyvalent metal salt of the acidphosphate esters has not been purified previously.

Specific examples of metal-containing organic phosphate complexes whichare disclosed in detail in US. Patent 2,820,723 and which are useful asingredient (B) herein are shown in Table 1.

Additional examples of metal-containing organic phosphate complexesuseful as ingredient (B) herein are as follows:

EXAlMlPl/E B-l In a flask equipped with a stirrer, 576 parts (3 moles)of heptylphenol and 114 parts (0.5 mole) of 2,2-bis-(parahydroxyphenyl)propane are introduced and heated to C. While the whole is stirredvigorously, 222 parts (1 mole) of P 8 is added gradually over a periodof 3 hours and heating is continued for an additional 3 hours.Filtration of the mass yields the complex phosphorodi thioic acid, whichis diluted with an equal weight of toluene to facilitate handling.

1376 parts of the toluene solution of the acid is mixed with 75 parts ofZinc oxide and 5 parts of water. The whole is heated for 5 hours at 6065C. and then filtered to yield a filtrate which is a 51.2 percentsolution of the zinc phosphorodithioate in toluene. Treatment of this a52.4 percent solution in toluene.

7 zinc phosphorodithioate with an equivalent amount (658 parts) of butylepoxystearate for 2 hours at 50-60 C. yields the desired zinc-containingorganic phosphate complex in solution in toluene.

EXAMPLE 13-2 A mixture of 520 parts (4.0 equivalents) of isooctylalcohol and 268 parts (4.0 equivalents) of dipropylene glycolis reactedwith 385 parts (1.73 moles) of phos: phorus pentasulfide for 8 hours at60-68 C. The resulting phosphorodithioic acid (1,110 parts) is dilutedwith 1,570 parts of benzene and neutralized with a percent excess ofzinc oxide (147 parts) for 7 hours under reflux, the water ofneutralization being removed as formed by means of a side-arm watertrap. Filtration yields 2,710 parts of a benzene solution of the zincphosphorodithioate, from which benzene is removed by heating to 93 C./50mm. Hg. The substantially benzene-free zinc phosphorodithioate (1,235parts) is blended with 250 parts of aromatic petroleum spirits boilingin the range 3l6-349 F. and then mixed with an equivalent amount (1,425parts) of butyl epoxystearate over a one hour period at 40-50 C. Theresulting zinc-containing organic phosphate complex has the followinganalysis? Phosphorus percent 3.65

'EIQAJMPIIJE 13-3 A mixture of 520 parts (4.0 equivalents) of isooctylalcohol and 268 parts (4.0 equivalents) of dipropylene glycol in 1,031parts of toluene is introduced into a flask and 243 parts (1.71 moles))of phosphorus pentoxide is introduced portionwise over a period of 2hours. The exothermic nature of the reaction causes the temperature ofthe mass to rise to about 60 C. Thereafter, the whole is heated for 4hours at 60 C. to yield the desired oxyphosphate esters as a 50 percentsolution in toluene.

1000 parts of the aforesaid toluene solution is reacted with 83 parts ofzinc .oxide and5 parts of Water for 5.5 hours at 40-45 C. Filtration ofthe mass yields 1,050 parts of the desired zinc-containing organicphosphate as 390 parts (0.59 equivalent) of the toluene solution of thezinc-containng organic phosphate is reacted with 422 parts (0.53equivalent) of 85 percent butyl epoxystearate over a 6-hour period at50-60 C. Filtration of the reaction mass yields the desiredzinc-containing organic phosphate complex as a 69.7 percent solution intoluene. It shows the 'follow-, Qf

contain substituent groups such as, e.g., chloro, fluoro,

ing analysis:

. .Percent.

Phosphorus 2.3 Zinc 2.04

toluene. It shows the following analysis:

Percent Phosphorus 4.26 Zinc 5.05

INGREDIENT (C) Ingredient (C), the metal-free organic phosphate complex,is described in detail in co-pending application Ser. No. 50,844, filedAugust 22, 1960. In brief, this ingreclient is prepared by mixing onemole of phosphorus pentoxide, from about 0.2 to about 12.5 moles of acopolyrner of allyl alcohol and a styrene, and from about 0.3 to about5.0 moles of an alkylphenol, and heating said mixture at a temperature,within the range from about 75 C. to about 150 C.

Ordinarily the reaction is carried out in a solvent and the solvent thenremoved, if desired, by distillation when the reaction is completed.Suitable solvents for this reac tion include, e.g., xylene, benzene,cyclohexane, chlorobenzene, ethylene dichloride, and dioxane. Otherinert, relatively volatile solvents (so as to afford easy removal fromthe product mixture) may also be used. The reaction may also be carriedout in the absence of a solvent and in such cases there is the obviousadvantage of not having to remove the solvent when the reaction iscompleted.

The reaction of the process appears to involve first a reaction betweenphosphorus pentoxide and the copolyrner of allyl alcohol and a styrene,followed then by reaction of this intermediate product with thealkylphenol. Presumably this latter reaction is a transesterification.The reaction mixture is at first cloudy and viscous, but as it proceedsthe cloudiness and viscosity disappear and the final product mixture isa relatively clear solution. The optimum reaction time is about 4 to 6hours, although a suitable product can be obtained at any point within aperiod of from about 1 to about 10 hours.

The copolymer of allyl alcohol and a styrene preferably is a lowmolecular Weight copolymer prepared from an approximately equimolarmixture of the two monomers. The molecular weight of the copolyrnershould be within the range from about 750 to about 1,500, preferablyabout 1,1001,150. The styrene monomer may be styrene itself, and mostusually it is, or it may be any of the various substituted styrenes suchas monochloro styrene, alkyl-substituted styrene, and alpha-substitutedstyrenes in which latter the substituent is an alkyl group, preferably'amethyl group.

The alkylphenol reactant may be either a mono-alkyl or a poly-alkylphenol. The alkyl groupsmay be of any size, ranging from methyl'up toalkyl groups derived from olefin polymers having molecular weights ashigh as 50,000 or more. Preferably the alkylphenol is a monoalkylphenolinwhich the alkyl group contains from 1 to about 30 carbon atoms,preferably at least about 4 carbon atoms. Typical examples of usefulalkylphenols include, e.g., ortho, meta, and para-cresols; ortho, meta,and paraethyl phenols; para-isopropylphenol, para-tertiary butylphenol,para-tertiary amylphenol, heptylphenol, diisobutylphenol, n-decylphenol,wax alkylated alpha-napthol, wax- 20 to about carbon atoms. Thealkylphenol may also nitro, alkoxy, sulfide, nitroso, etc.

The process is carried out simply by mixing the specified reactants,preferably with a solvent, and heating the resulting solution at atemperature within the range from about 75 C. to about 150 C. until thereaction is complete. As indicated earlier, the first stages of theoverall reaction produce a cloudy, thickened reaction mixture and as thereaction proceeds this is changed to a relatively clear, non-viscoussolution. Several illustrative examples follow:

A mixture of 1,412 parts (1.2 moles) of a 1:1 molar copolyrner of allylalcohol and styrene having an average molecular weight of about 1,100and available commercially under the trade designation Polyol X-450, 168parts (1.0 mole) of para-tertiary amylphenol, 68 parts (0.5 mole) ofphosphorus pentoxide, and 1,648 parts of xylene solvent is prepared atroom temperature and then heated at the reflux temperature, ca. 141 C.,for 6 hours. The reaction mixture is stirred throughout this period andwater of reaction is removed by means of a side-arm water trap. At theend of this time the xylene 'is removed bydistillation to yield aplastic, non-viscous mass. This residue, while still hot, i.e., aboutC., is diluted with 824 parts of isobutyl alcohol. The product, a 65percent solution of the metal-free organic phosphate complex in isobutylalcohol, shows the following analysis:

Phosphorus percent 1.16

Acid No. (phenolphthalein indicator) 22.6.

A mixture of 313 parts (0.284 mole) of Polyol X450, 314 parts (0.786mole) of mono-(polyisobutene-substituted)phenol wherein thepolyisobutene substituent contains an average of about 22 carbon atoms,31 parts (0.218 mole) of phosphorus pentoxide, and 660* parts of xyleneis heated to the reflux temperature, ca. 140 C., and maintained at thistemperature for 6 hours while water is removed by means of a side-armwater trap. Substantially all of the Xylene is removed by distillationof the mass at 140 C./20 mm. Hg. and then the residue is diluted with350 parts of isobutyl alcohol. The product, a 65 percent solution of themetal-free organic phosphate complex in isobutyl alcohol, shows thefollowing analysis:

Phosphorus percent 1.35 Acid No. (bromphenol blue indicator) 16.7

Additional examples of metal-free organic phosphate complexes are shownin Table 3. They are prepared in the same manner set forth in ExampleC-2 using the indicated quantities of reagents.

the purposes of the present invention, it is also desirable in certaininstances, to acylate ingredient (C) with a high molecular weightunsaturated aliphatic carboxylic acid containing at least 12 carbonatoms and/or ester thereof such as, e.g., linoleic acid, linolenic acid,linseed oil, tung oil, tung oil acids, methyl linoleate, ethyllinolenate, chloroleic acid, phenyloleic acid, oleic acid, behenolicacid, palmitolic acid, ricinoleic acid, recinstearolic acid, andmixtures of any of the foregoing. Especially preferred are theunsaturated aliphatic carboxylic acids and/or esters which contain atleast two double bonds such as linoleic and linolenic acids.

The acylation can be carried out in any one of several ways such as, forexample: adding the unsaturated aliphatic carboxylic acid and/or esterthereof to the reaction mixture prepared for ingredient (C) and thencarrying out the reaction in the manner indicated earlier; heating thecopolymer or allyl alcohol and a styrene with the unsaturated aliphaticcarboxylic acid and/ or ester thereof for 0.5-12 hours at 80-200 C. inthe presence, optionally, of an esterification catalyst and then usingsuch acylated copolymer as the polymeric reactant in the preparation ofingredient (C); or heating the unsaturated aliphatic carboxylic acidand/ or ester with ingredient (C) for 0.5-12 hours at 80200 C.

In each of the foregoing procedures, the amount of the unsaturatedaliphatic carboxylic acid and/or ester used should be within the rangefrom about 0.5 to about 4 moles, preferably from about 1.0 to about 3moles, per mole of the copolymer of allyl alcohol and a styrene.

The following examples set forth specific modes of preparing an acylatedingredient (C). The acid no. in each instance is determined usingbromphenol blue as an indicator.

10 EXAMPLE C-9 431 parts (0.375 mole) of Polyol X-450, 140 parts (0.5mole) of linoleic acid, and 0.2 part of para-toluene sulfonic acid(esterification catalyst) are dissolved in 864 parts of xylene. Thewhole is refluxed for 6 hours and the water of esterification is removedby means of a side-arm water trap. To the resultant acylated Polyol X450in xylene are added 231 parts (1.41 moles) of para-tertiary amylphenoland 71 parts (0.5 mole) of phosphorus pentoxide. The reaction mixture isheated for 6 hours at the reflux temperature to yield the desiredacylated, metalfree, organic phosphate complex as a 50 percent solutionin xylene. It shows the following analysis:

Phosphorus percent 1.86 Acid No. 36

EXAMPLE C-9A 210 parts (0.75 mole) of linoleic acid, 288 parts (0.25mole) of Polyol X-450, 283 parts of xylene solvent, and 4 parts of paratoluenesulfonic acid catalyst are introduced into a reaction vessel andstirred thoroughly. The whole is then heated to about 143 C., andmaintained at this temperature for 4 hours while water of esterificationis removed by means of a side-arm water trap. The crude acylated PolyolX-450 thus obtained is washed with 500 parts of water to remove theesterification catalyst and then it is dried by azeotropic distillation,returning the xylene by means of a side-arm water trap.

949 parts (0.24 mole) of the acylated Polyol X450, 79 parts (0.48 mole)of para-tertiary amylphenol, 36 parts (0.25 mole) of phosphoruspentoxide, and parts of xylene solvent are reacted at the refluxtemperature (ca. 143 C.) for 6 hours.

The resulting 50 percent solution in xylene of the desired acylatedorganic phosphate complex shows the following analysis.

Phosphorus percent 1.28

Acid No. 98

EXAMPLE c-lo 575 parts (0.5 mole) of Polyol X-450, 468 parts (0.5 mole)of boiled linseed oil, 164 parts (1.0 mole) of paratertiary amylphenol,71 parts (0.5 mole) of phosphorus pentoxide, and 1278 parts of xyleneare placed in a flask and stirred vigorously. The whole is refluxed for6 hours while water is removed by means of a side-arm water trap. Theproduct, a 50 percent solution of the desired acylated organic phosphatecomplex in xylene, shows the following analysis.

Phosphorus percent 1.15 Acid No. 84

EXAMPLE C-ll 575 parts (0.5 mole) of Polyol X450, 598 parts (2.0 moles)of methyl linoleate, 164 parts (1.0 mole) of paratertiary amylphenol, 71parts (0.5 mole) of phosphorus pentoxide, and 1408 parts of xylenesolvent are introduced into a reaction vessel and stirred vigorously.The whole is then heated for 6 hours at the reflux temperature whilewater is removed by means of a side-arm water trap. The product, a 50percent solution of the acylated organic phosphate complex in xylenesolvent, shows the following analysis.

Phosphorus percent 0.99 Acid No. 72

EXAMPLE C-12 1,150 parts (1.0 mole) of Polyol X-450, 852 parts (3.0moles) of crude linoleic acid derived from tall oil, 2,400 parts ofxylene solvent, 328 parts (2.0 moles) of paratertiary amylphenol, and142 parts (1.0 mole) of phosphorus pentoxide are introduced into areaction flask fitted with a side-arm water trap. The whole is heatedfor 4.5 hours at the reflux temperature to yield the product, a 50percent solution of the acylated organic phosphate complex in xylene. Itshows the following analysis.

719 parts (0.625 mole) of Polyol X-450, 164 parts (1.0 mole) ofpara-tertiary amylphenol, and 71 parts (0.5 mole) of phosphoruspentoxide, and 952 parts of xylene solvent are introduced into a flaskfitted with a stirrer and a side-arm water trap. The whole is refluxedfor 6 hours while the water of reaction is removed as formed.

494 parts (0.641 mole) of the resulting organic phosphate complex isacylated with 179 parts (0.641 mole) of linoleic acid over a 7 hourperiod at 154 C. The water of esterification is removed as formed bymeans of a sidearm water trap. The product, a 63 percent solution of theacylated organic phosphate complex in xylene, shows the followinganalysis.

Phosphorus percent 1.02 Acid N0. 51

' of two or more such ingredients with a viscosity-reducing amount of avolatile solvent so as to facilitate the application of the coatingcomposition to metal surfaces. Solvents useful for this purpose includethose which are commonly employed in the paint and lacquer industriessuch as, for example, petroleum hydrocarbon solvents such as, petroleumaromatic spirits; alcohols such as, e.g., methyl, ethyl, propyl, butyl,and amyl alcohols; ketones .such as, e.g., acetone, diethyl ketone,methyl isobutyl ketone, methyl ethyl ketone, etc.', the lowerchlorinated alkanes such as, e.g., ethylene dichloride,1,2-dichloropropane, butyl chloride, etc.; aromatic hydrocarbons suchas,

e.g., benzene, toluene, xylene, mesitylene, etc.; and'aliphatic etherssuch as, e.g., diisopropyl ether, diisobutyl ether, and the like. Incertain instances it is desirable to use mixtures of 2 or more solvents.The aromatic petroleum spirits useful in adjusting the viscosity of thecompositions of the present invention are available from variouspetroleum refiners. These petroleum-derived solvents generally boil inthe'range from about 300-400 F. and have a Kauri-butanol value fromabout 50 to about 125. An economical, commercially available mixture ofaromatic petroleum spirits boils in the range 316349 F. and has aKauri-butanol value of about 91.

Although the proportions of the several ingredients are not particularlycritical, best results from the standpoint of economy, ease ofapplication, and weldability of the coated metal surface are obtainedwhen one uses a composition prepared from the mixture of from about 300to about 450 parts, preferably from about 350 to about 400 parts, ofingredient (A), the zinc dust; from about to about 70 parts, preferablyfrom about 10 to about 40 parts, of ingredient (B), the,metal-containing organic phosphate complex; and from about 6 to about 80parts, preferably from about 12 to about 60 parts, of ingredient (C),the metal-free organic phosphate complex. To this mixture there may beadded, optionally, a small amount,

' generally from about 1 to about 10 parts, more often from about 2 toabout 6 parts, of a pigment-suspending agent and at least about 10parts, preferably from about 15 to about 120 parts, of aviscosity-reducing solvent. The use of a pigment-suspending agent,although not absolute- In addition to these characterizing 12 .lyessential, is required if settling of the zinc dust is to be avoided. Inthe absence of this agent, the composition must be stirred at frequentintervals after preparation and during use. Thus, for obviouspracticalreasons it is highly desirable to include a pigment-suspending agent inthe compositions of this invention.

The order of mixing the ingredients of the composition is notparticularly critical. It is generally most convenient, however, to millthe pigment-suspending agent, is used, in all or a portion of thesolvent-diluted ingredient (B), the metal-containing organic phosphatecomplex, by. means of a ball mill or other conventional paint-dispersingequipment. This mixture is then removed to another vessel equipped withmeans for vigorous stirring and ingredient (A), the powdered zinc, andthe balance, if any, of ingredient (B) are added and stirred well. Asmall proportion of solvent, either added directly to the vesselcontents or present in ingredient (B) serves to facilitate the mixingoperation. After the mixture has been stirred for a sufficient time tobecome homogeneous, ingredient (C), the metal-free organic phosphatecomplex, is added while the whole is stirred vigorously. The consistencyof the mass is then adjusted by the addition, if desired, of a furtheramount of solvent so as to yield a composition which has a viscositywell-suited for the particular method by which it is to be applied to ametal surface. The application to a metal surface may be made by any oneof the methods commonly used in the paint industry such as dipping,brushing, roller-coating, flow-coating, or spraymg.

Although any of the various ingredients (A) through (C) describedearlier may be used in compounding the compositions of the presentinvention, certain ingredients and combinations thereof are preferredfor reasons of their commercial availability and economy. Thus, forexample, a very usful and economical group of compositions of thisinvention contain as essential ingredients: (A) From about 300 to about450 parts, preferably from about 350 to about 400 parts, of powderedzinc;

(B) From about 5 to about 70 parts, preferably from about 10 to about 40parts, of a zinc-containing organic phosphate complex prepared by theprocess which comprises the reaction of (I) A zinc salt of the acidphosphate esters derived from the reaction of a phosphorus-containingre-- agent selected from the group consisting of phosphorus pentasulfideand phosphorus pentoxide with a mixture of a monohydric alcohol and from0.25 to 4.0 equivalents of a polyhydric alcohol, and

(II) At least about 0.1 quivalent of an aliphatic epoxide;

(C) From about 6 to about parts, preferably from about 12 to about 60parts, of a metal-free organic phosphate complex prepared by the processwhich comprises mixing 1 mole of phosphorus pentoxide, from about 0.2 toabout 12.5 moles of a copolymer of allyl alcohol and styrene having anaverage molecularvweight within the range from about 750 to about 1500,from about 0.3 to about 5.0 moles of a mono-alkyl phenol containing atleast about 5 carbon atoms in the alkyl group, and heating said mixtureat a temperature withinthe range from about 75. to about 150 C.;

(D) At least about 10 parts, preferably from about 15 to about parts, ofa volatile solvent selected from the group consisting of petroleumhydrocarbon solvents, alcohols, ketones, lower chlorinated alkanes,aromatic hydrocarbons, and aliphatic ethers and, optionally,

(E) From about 1 to about 10 parts, preferably from about 2 to about 6parts, of castor wax.

Specific illustrations of the preparation of compositions of thisinvention are as follows. All parts are by weight unless otherwiseindicated.

EXAMPLE I 4.0 parts of a commercial grade of castor wax known as ThixcinR is dispersed in 10 parts of the product of 13 Example B3 and 18 partsof Solvent X (petroleum aromatic spirits boiling in the range 316349 F.and having a kauri-butanol value of 91). After the castor wax isthoroughly dispersed (15 minutes is normally required when aconventional paint shaking machine is used), the whole is transferred toa vessel equipped with a propeller-type stirring device and 44 partsmore of the product of Example B-3 and 375 parts of powdered zincpassing 325-mesh screen are added. The ingredients are stirredvigorously until they form a homogeneous mass. Thereafter, 18.75 partsof the product of Example C-2 and parts of Solvent X are added to thecontents of the Vessel and the whole is stirred until all of theingredients will be applied directly to the bare metal surface to beprotected. In certain applications however, where superior corrosionresistance is sought, the metal may be pretreated with a metalpassivating solution such as, e.g., a dilute .chromic acid solution, oran aqueous phosphating solution such as, e.g., aqueous acidic zincdihydrogen phosphate, aqueous acidic manganese dihydrogen phosphate, andthe like. Such metal passivating or phosphating techniques arewell-known and are described, for example, in US. Patents 1,206,075;1,247,668; 1,305,331; 7,485,025; 1,610,362; 1,980,518; 2,001,754;2,901,385; 2,846,342; 2,868,682; 2,901,437; and 2,876,150. A very usefuland effective class of aqueous phosphating solutions containing asessential ingredients zinc ion, phosphate ion, nitrate ion, and calciumion are described in U.S. application Ser. No. 373,449, filed August 5,1953.

In addition to the pretreatment of the metal surface, it may also bedesirable in certain instances, particularly where decorative effectsare sought, to top-coat the dried film of a composition of thisinvention with a paint, paint primer, lacquer, or enamel. Thecompositions of this invention serve as an excellent base for such top-Table 4 Metal-containing organic Metal-free organic Pigment-suspendingagent Solvent added Zinc phosphate complex phosphate complex ExamplePowder,* No. parts Product of Parts Product of Parts Identity PartsIdentity Parts EX. No. Ex. N 0.

375 17. 5 31. 4 Thixcin R 440 43.1 46. 2 do 440 21. 5

375 52 .do 8.1 Solvent X 20. 7 310 65 9 Zinc stearate 2 Ethglene dichlonc. 340 5. 5 15 Cadmium stea- 9 Xylene 20 rate. M ethylisobutyl. 410 2325 Almtninum stea- 7 Mesitylene 42 re e.

360 20 Thixcin R 1. 5 {gi fg fg ether- *Passing 325-mesh screen.

The compositions of this invention are generally applied to the metalsurface to be protected in an amount sufficient to yield a dried filmthickness of from about 0.5 t about 10 mils and preferably from about 1to about 3 mils. After application to the metal surface, the compositionmay be dried by any one of the various methods commonly employed in thepaint and lacquer industry such as air-drying at ambient temperature,drying in a current of hot air, baking in an oven, or baking under abank of infra-red lamps. In general, best results from the standpoint ofgood adherence and corrosion protection are obtained with thecompositions of this invention when a film thereof is air-dried atambient temperature. Oven-baking procedures, which are useful in someinstances, however, call for exposure of the coated metal surface totemperatures in the range of 250-450" F. for a period ranging from about1 minute to about 1 hour. The lower baking temperatures generallyrequire longer periods of time than the higher baking temperatures; for

example, typical procedures call for baking at 400 F.

for 2 minutes, or 15 minutes at 360 F., or 45 minutes at In mostinstances the compositions of this invention coats in that they inhibitthe deterioration of the underlying base metal and thereby remove theprincipal cause of blistering, flaking, and other forms of loss ofcoating adhesion. The above discussion regarding pretreatment of themetal surface and top-coating of the dried film of the compositions ofthis invention is not to be construed as indicating that suchpretreatments or post-treatments are at all required for adequateprotection of metal sur faces. It has been offered merely to point outthe versatility of the present compositions in adhering well to modifiedmetal surfaces and in providing an excellent paint base in applicationswhere a top-coat must be applied.

Tests were carried out to deter-mine the efiicacy of the presentcompositions in retarding corrosion of ferrous metal surfaces. In all ofthe tests, 4-inch x 8-inch panels of clean, solvent-degreased, 20-gaugeSAE 1020 coldrolled steel prepared according to ASTM procedure D 609-52were used to receive films of the coating compositions of thisinvention. The compositions were brushed on the steel panel and dried inthe indicated manher to provide a film having a thickness of 15:02 mils.

. is somewhat less than the given value would indicate.

The prepared panels were then subjected to a salt fog corrosion test.

The apparatus used for this test is described in ASTM pnocdeure B ll757T. It consists of a chamber in which a mist or fog of aqueous sodiumchloride is maintained in contact with the test panels for apredetermined time at 95;L2" F.

In the 120-hour test, the coating on the panel is pierced with a pointedinstrument to yield a vertical scribe beginning one inch from the top ofthe panel and ending one inch from the bottom thereof. The panel is thenplaced in the salt fog chamber for 120 hours and removed for inspection.The creep rating is the average loss of coating from each side of thescribe expressed as an integer which represents the number ofthirty-seconds of an inch. The panel is also visually inspected for rustand the amount thereof is reported as percent of area rusted.

In the 250-hour test, duplicate unscribed, coated panels are placed inthe salt fog chamber for 250 hours and then removed for inspection. Theamount of rust on each panel is noted and the average for the two panelsis reported as average per cent of area rusted. An unprotected steelpanel becomes rusted over its entire surface (i.e., fails) in one houror less when subjected to this test.

Although no specific test standards have yet been promulgated byindustry, past experience indicates that a composition which holdscorrosion to a value not greater than about 15 percent in the 250-hourtest and, optionally, has a creep rating not greater than about 4 willperform satisfactorily in the field.

The test results obtained on a nuumber of compositions of this inventionare set forth in Table 5.

Table 5 Salt fog corrosion test results Composition of Ex. N 0. Averagepercent of area rusted Panel preparation Test, hours Creep rating 1A=air-dried at ambient temperature. B =baked 15 minutes at 360 F. 2 Aminus sign after a value denotes that the percent of area rusted Theinspection for rust does not include the so-called white corrosion whichresults from the conversion of the zinc powder to zinc salts and whichis expected in zine-filled paints that protect ferrous surfaces by thesacrificial consumption of zinc metal.

3 These panels were coated by means of a sprayer.

In addition to their utility as protective coating materials for ferrousmetals, the compositions of this invention are also useful in protectingnon-ferrous metals and alloys thereof such as aluminum, magnesium,magnalium, copper, brass, bronze, white metal, Dowmetal, etc., againstcorrosion. They are also useful as protective coating materials ongalvanized ferrous surfaces, on

plated metal surfaces such as, e.g., copper-plated, nickelplated, andcadmium-plated ferrous surfaces, and on phosphated metal surfaces.Particularly fine results are obtained when the coating compositions ofthe present invention are applied over a metal surface which has beenphosphated by means of a novel aqueous phosphating solution containingas essential ingredients zinc ion, phosphate ion, nitrate ion, and acation selected from the group consisting of lithium, beryllium,magnesium, calcium, strontium, cadmium, and barium. Such phosphatingsolutions, which provide a dense, adherent, microcrystalline oramorphous phosphate coating upon the metal substrate, are described indetail in copending U.S. application Serial No. 373,449, filed August10, 1953,, now Patent No. 3,090,709. It is intended that the entiredisclosure of Serial No. 373,449, now Patent No. 3,090,709, beincorporated herein by reference.

What is claimed is: 1. A fluid composition adapted to form a protectivecoating on metals which contains as essential ingredients: (A) fromabout 300 to about 450 parts of finely divided 1 zinc,

(B) from about 5 to about 70 parts of a metal-containing organicphosphate complex prepared by the process which comprises the reactionof (I) a polyvalent metal salt of the acid phosphate.

esters derived from the reaction of a phosphoruscontaining reagentselected from the group consisting of phosphorus pentasulfide andphosphorus pentoxidc with a mixture of monohydric and polyhydricalcohols, and

(II) at least about 0.1 equivalent of an organic epoxide having from 2to about 57 carbon atoms, and

(C) from about 6 to about 80 parts of a metal-free organic phosphatecomplex prepared by the process which comprises mixing one mole ofphosphorus pentoxide, from about 0.2 to about 12.5 moles of a copolymerof allyl alcohol and a styrene, and from about 0.3 to about 5.0 moles ofan alkylphenol, and heating said mixture at a temperature within therange from about 75 C. to about 150 C. v

2. A composition in accordance with claim 1 further characterized inthat ingredient (C) has been acylated with a high molecular weightcarboxylic acid compound selected from the group consisting ofunsaturated aliphatic carboxylic acids containing at least 12 carbonatoms and esters thereof. Y Y

3. A composition in accordance with claim 1 further characterized inthat it additionally contains a pigmentsuspending agent selected fromthe group consisting of castor wax and polyvalent metal stearates.

4. A composition in accordance with claim 1 further characterized inthat the polyvalent metal salt of (B)I is a zinc salt.

5. A composition in accordance with claim 1 further I characterized inthat the alkylphenol of (C) is a monoalkyl phenol 6. A fluid compositionadapted to form, a protective coating on metals which contains asessential ingredients:

(A) from about 300 to about 450 parts of powdered (B) from about 5 toabout 70 parts of a zinc-containing organic phosphate complex preparedby the process which comprises the reaction of (I) a zinc salt of theacid phosphate esters. derived from the reaction of aphosphorus-containing reagent selected from the group consisting ofphosphorus pentosulfide and phosphorus pentoxide with a mixture ofmonohydric alcohol and from 0.25 to 4.0 equivalents of a polyhydricalcohol, and

(II) at leastabout 0.1 equivalent of an aliphatic epoxide having from 2to about 57 carbon atoms,

(C) from about 6 to about parts of a metal-free organic phosphatecomplex prepared by the process which comprises mixing one mole ofphosphorus pentoxide, from about 0.2 to about 12.5 moles of a copolymerof allyl alcohol and styrene having an average molecular weight withinthe range of from about 750 to about 1500, from about 0.3 to about 5.0moles of a mono-alkyl phenol containing at least about 4 carbon atoms inthe alkyl group, and heating said mixture at a temperature within therange of from about 75 C. to about 150 C., and

(D) at least about 10 parts of a volatile solvent selected from thegroup consisting of petroleum hydrocarbon solvents, alcohols, ketones,lower chlorinated alkanes, aromatic hydrocarbons, and aliphatic ethers.

7. A composition in accordance with claim 6 further characterized inthat it additionally contains from about 1 to about 10 parts of castorwax.

8. A composition in accordance with claim 6 further characterized inthat the powdered zinc of (A) passes 325- mesh screen.

9. A composition in accordance with claim 6 further characterized inthat the zinc salt of (B)I is the zinc salt of the acid phosphate estersderived from the reaction of a phosphorus-containing reagent selectedfrom the group consisting of phosphorus pentasulfide and phosphoruspentoxide with a mixture of about equivalent amounts of isooctyl alcoholand dipropylene glycol.

10. A composition in accordance with claim 6 further characterized inthat the aliphatic epoxide of (B)-II is butyl epoxystearate.

11. A composition in accordance with claim 6 further characterized inthat the aliphatic epoxide of (B)-II is beta-propiolactone.

12. A method of inhibiting the corrosion of a metal surface whichcomprises applying thereto a film of the fluid composition of claim 1.

13. A metal article the metal surface of which has been protectedagainst corrosion in accordance with the method of claim 12.

References Cited by the Examiner UNITED STATES PATENTS 2,548,048 4/ 51Olsen 106290 2,820,723 l/58 Le Suer. 3,055,865 9/62 Craig 106l4 FOREIGNPATENTS 208,194 10/56 Australia.

ALEXANDER H. BRODMERKEL, Primary Examiner.

MORRIS LIEBMAN, LESLIE H. GASTON, Examiners.

1. A FLUID COMPOSITION ADAPTED TO FORM A PROTECTIVE COATING ON METALSWHICH CONTAINS AS ESSENTIAL INGREDIENTS: (A) FROM ABOUT 300 TO ABOUT 450PARTS OF FINELY DIVIDED ZINC, (B) FROM ABOUT 5 TO ABOUT 70 PARTS OF AMETAL-CONTAINING ORGANIC PHOSPHATE COMPLEX PREPARED BY THE PROCESS WHICHCOMPRISES THE REACTION OF (I) A POLYVALENT METAL SALT OF THE ACIDPHOSPHATE ESTERS DERIVED FROM THE REACTION OF A PHOSPHORUSCONTAININGREAGENT SELECTED FROM THE GROUP CONSISTING OF PHOSPHORUS PENTASULFIDEAND PHOSPHORUS PENTOXIDE WITH A MIXTURE OF MONOHYDRIC AND POLYHYDRICALCOHOLS, AND (II) AT LEAST ABOUT 0.1 EQUIVALENT OF AN ORGANIC EPOXIDEHAVING FROM 2 TO ABOUT 37 CARBON ATOMS, AND (C) FROM ABOUT 6 TO ABOUT 80PARTS OF A METAL-FREE ORGANIC PHOSPHATE COMPLEX PREPARED BY THE PROCESSWHICH COMPRISES MIXING ONE MOLE OF PHOSPHORUS PENTOXIDE, FROM ABOUT 0.2TO ABOUT 12.5 MOLES OF A COPOLYMER OF ALLYL ALCOHOL AND A STYRENE, ANDFROM ABOUT 0.3 TO ABOUT 5.0 MOLES OF AN ALKYLPHENOL, AND HEATING SAIDMIXTURE AT A TEMPERATURE WITHIN THE RANGE FROM ABOUT 75*C. TO ABOUT150*C.